二乙基二硫代氨甲酸银体系流动注射法测定砷

本文设计了一种ＡｇＤＤＣ流动注射－分光光度法测定砷的系统。该系统采用自制的氢化物发生及吸装置，将液体流路和载气流路结合在一起。     

Substoichiometric isotope dilution determination of manganese in biological smples using 2-thenoyltrifluoroacetone in isobutyl methyl ketone

A substoichiometric isotope dilution method was developed for the determination of microgram amounts of manganese. The method involves the use of carrier-free ⁵⁴Mn with Mn(II) carrier and its complexation with 2-thenoyltrifluoroacetone (TTA) at pH 8.5, the complex then being extracted into isobutyl methyl ketone. A minimum of 50 ng of manganese can be determined. The method was applied to the determination of manganese in several standard reference materials and biological samples such as tea leaves, spices and condiments. The method is simple and fast and yields results with high accuracy and precision.     

Y掺杂对氢氧化镍电极高温性能的影响

合成了内掺稀土元素Y的β-Ni(OH)2和α-Ni(OH)2材料, 并通过XRD、TEM、CV 和充放电测试等方法研究了Y元素对这两种晶型活性材料的结构、形貌以及高温电化学性能方面的影响, 发现Y元素可显著提高β-Ni(OH)2和α-Ni(OH)2材料的高温性能, 且作用机理相同, 均是通过提高析氧过电位来改善镍电极的高温充电效率. 但是α-Ni(OH)2在高温下的相稳定性仍有待提高.     

Relativistic calculations on the ground and excited states of AgH and AuH in cylindrical harmonic confinement

The relativistic ground and low-lying excited state potential energy curves of AgH and AuH in the presence of a cylindrical harmonic confining potential were calculated using the multi-state multi-reference perturbation theory with the spin-free no-pair Hamiltonian obtained via the third-order Douglas–Kroll transformation, incorporated with the full two-electron Breit–Pauli spin–orbit operator. The spectroscopic parameters were obtained for both the scalar- and quasi-relativistic potentials. The spin–orbit coupling constants were calculated for several strengths of the confining potential, and the effects of the applied potential on the coupling constants were analyzed using configuration interaction. This paper is dedicated to Serafín Fraga—colleague, mentor, and friend.     

Synthesis and manganese complexes of pentagonal bipyramidal ligands: N,N′-disubstituted pentaaza macrocycles

Two novel heptadentate ligands, pentaaza macrocycles with two pendant xpyridyl and phenol groups, were prepared and the crystal structure of the manganese(II) complex of N,N′-bis(2-pyridylmethyl)-pentaaza macrocycle revealed a pentagonal bipyramidal geometry.     

Non-solvated aluminum hydride. Crystallization from diethyl ether-benzene solutions

Crystallization of non-solvated aluminum hydride from a diethyl ether-benzene mixed solvent was studied. The desolvation of AlH₃·(Et₂O)_x etherate in solution and the crystallization of α-AlH₃ during polythermal heating of the solution occur only in the presence of ≥10 wt.% LiAlH₄. The process is multistage, and the crystallization begins with the formation of the AlH₃·0.25Et₂O solvate, which recrystallizes in the solid phase into γ-AlH₃ and then α-AlH₃. Four crystalline modifications of aluminum hydride were characterized by X-ray diffraction and electron microscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1259–1265, July, 2007.     

二茂锆羧酸配合物的合成——二茂锆氢化物与α,β—不饱和酸或钠盐反应的研究

本文研究了Cp_2ZrH_2与丙烯酸和Cp_2Zr(H)Cl与丙烯酸钠、巴豆酸钠的反应。产物由IR 1~H和~(13)CNMR、ESR谱、气相色谱以及化学方法分析鉴定。产物水解得到与底物相应的饱和酸.用~1H NMR方法考察了Cp_2ZrH_2与丙烯酸的反应过程,用IR方法考察了Cp_2Zr(H)Cl与丙烯酸钠的反应过程。实验结果表明,上面两种反应首先消除H_2或NaCl,形成锆氧健,然后碳碳双键还原生成二茂锆羧酸盐配合物,其中羧酸根离子与二茂锆桥式双齿配位。     

丹宁纤维素富集-氢化物发生ICP-AES同时测定水中痕量锗

研究了丹宁纤维素富集10~(-11)g/ml级锗的条件,并考察了地下水中36种共存离子对磷酸介质中氢化物发生ICP-AES测定锗的干扰和消除,应用于测定地下水中的超痕量锗,结果满意,检出限为15ng/L。     

醇脱氢酶结构和作用机理研究进展

介绍了醇脱氢酶的种类, 酵母醇脱氢酶和肝醇脱氢酶等两类常用的醇脱氢酶的物理化学性质和活性位点结构. 归纳了对肝醇脱氢酶和酵母醇脱氢酶作用机理的研究, 重点评述了醇脱氢酶催化反应中的两个关键步骤质子转移和氢化物转移过程机理的研究进展.     

Mn(III)-based C-C bond formation: regioselective α′-allylation of various α,β-unsaturated, α and β-alkoxy α,β-unsaturated ketones

The Manganese(III)-based regioselective α′-keto radical generation of unsaturated ketones is a versatile synthetic procedure with broad applicability. The generated α′-keto radical slowly creates a metal enolate in a solvent at reflux. The resultant metal enolate affords the corresponding α′-allylated α,β-unsaturated ketones in good yields. This method is the first example of the metal mediated regioselective α′-allylation of α,β-unsaturated ketones. The ketones that have α or β-alkoxy groups also work efficiently.